Paramagnetic Molecular Semiconductors Combining Anisotropic Magnetic Ions with TCNQ Radical Anions.

We report the synthesis, magnetic properties, and transport properties of paramagnetic metal complexes, [Co(DMF)(TCNQ)](TCNQ) (), [La(DMF)(TCNQ)](TCNQ) (), and [Nd(DMF)(TCNQ)](TCNQ) () (DMF = ,-dimethylformamide, TCNQ = 7,7,8,8-tetracyanoquinodimethane). All three compounds contain fractionally charged TCNQ anions (0 < δ < 1) and mononuclear complex cations in which the coordination environment of a metal center includes several DMF molecules and one or two terminally coordinated TCNQ anions. The coordinated TCNQ anions participate in π-π stacking interactions with noncoordinated TCNQ anions, forming columnar substructures that provide efficient charge-transporting pathways.